US4557914A - Process for producing substances optically transparent to infrared rays - Google Patents

Process for producing substances optically transparent to infrared rays Download PDF

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Publication number
US4557914A
US4557914A US06/626,053 US62605384A US4557914A US 4557914 A US4557914 A US 4557914A US 62605384 A US62605384 A US 62605384A US 4557914 A US4557914 A US 4557914A
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United States
Prior art keywords
chalcogenides
chloride
reaction
chamber
dihydrogen
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US06/626,053
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English (en)
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Eros Modone
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Telecom Italia SpA
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CSELT Centro Studi e Laboratori Telecomunicazioni SpA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
    • C03B19/1415—Reactant delivery systems
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/041—Non-oxide glass compositions
    • C03C13/043—Chalcogenide glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/80—Non-oxide glasses or glass-type compositions
    • C03B2201/86—Chalcogenide glasses, i.e. S, Se or Te glasses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S501/00—Compositions: ceramic
    • Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
    • Y10S501/904—Infrared transmitting or absorbing

Definitions

  • My present invention relates to the production of substances that are optically transparent to infrared radiation and are usable in the manufacture of optical fibers or lasers and other radiation emitters.
  • silicon-based fibers and other electronic components it is convenient to use the well-known chemical-vapor-deposition (CVD) process; see, for example, commonly owned U.S. Pat. Nos. 4,389,230 and 4,414,164.
  • CVD chemical-vapor-deposition
  • silicon can be obtained from one of the following reactions performed in a high-temperature furnace:
  • Zinc sulfide and zinc selenide usable in fiber-optical technology for infrared transmissivity, are available in accordance with reactions
  • the CVD process is designed to minimize the problems of radiation absorption, e.g. intrinsically by substrate/impurity bonds and extrinsically through scattering by the presence of anomalous domains. These latter may result from grain dislocations in a crystalline substrate or, with a vitreous substrate, from crystalline zones or from separation of phases of different densities.
  • Redox reactions used in conventional CVD processes are sometimes accompanied by side reactions, involving different valence states, that give rise to undesired and often detrimental products.
  • Reaction (4) may result in the formation of ZnH groups in the ZnS matrix, with the zinc in its monovalent form. These groups present absorption bands within the infrared range of interest lying between 2 and 12 ⁇ .
  • the object of my present invention is to provide a modified CVD process which obviates the redox reactions yielding undesired compounds.
  • the modified CVD process comprises vaporizing one or more chalcogen compounds and of one or more salts of a metal or metalloid, preferably a halide, and subjecting the resulting vapors under nonreducing and nonoxidizing conditions to a double-substitution reaction producing a chalcogenide (other than an oxide) of the metal or metalloid referred to.
  • Chalcogens are members of the oxygen family in Group VIA of the Periodic Table, namely--besides oxygen--sulfur, selenium tellurium and polonium. I particularly contemplate the use of sulfur, selenium and tellurium for the practice of my present process in which I prefer their hydrides as a starting compound, i.e. H 2 S, H 2 Se or H 2 Te.
  • the salt serving as a reactant is preferably a chloride of the metal or metalloid whose sulfide, selenide or telluride is to be produced.
  • the double-substitution reaction eliminates the aforedescribed side reactions based on different valence states. It is particularly advantageous when the resulting chalcogenide is a high-boiling compound which during processing assumes a state of aggregation different from that of both the initial and residual reactants and byproducts, thereby facilitating the separation of the desired product.
  • the desired product is solid at the processing temperature, which ought to be much higher than the boiling point of the reactants, the process requires low energy and, with equilibrium shifting entirely toward the right-hand side of the reaction, operates with an efficiency close to 100%.
  • the metals and metalloids primarily usable in my process are arsenic, antimony, zinc, germanium, tin, lead, silicon and cadmium.
  • the resulting chalcogenides, especially sulfides have a wide transmission window in the infrared range, with low absorption coefficients and a theoretical attenuation of about 10 -2 dB/Km at 5-6 ⁇ .
  • Their thermal-expansion coefficient is 10 -6 /K which facilitates the drawing of optical fibers from glasses containing same.
  • Their refractive indices of about 2 makes them suitable for the manufacture of glass/plastic fibers with a stepped index of refraction.
  • FIGURE diagrammatically shows an installation for performing a modified CVD process as described above.
  • two boiling vessels 1 and 2 respectively generate vapors of a chalcogen hydride and a metal halide. These vapors are concurrently led to a reaction chamber 3 heated to a start-up temperature which causes them to interact, in a nonoxidizing and nonreducing atmosphere, to produce a desired metal chalcogenide whose melting point lies well above the chamber temperature and which therefore precipitates as a solid at an outlet 4.
  • the metal of course, could be replaced by a metalloid such as arsenic or silicon.
  • Arsenic trisulfide is produced by a double-substitution reaction given by
  • the hydrogen sulfide (or sulfur hydride) and the arsenic trichloride, respectively vaporized in vessels 1 and 2, have boiling points of about -60° C. and +63° C., respectively; chamber 3, to which their vapors are separately fed, is initially heated to about 200° C. to start up the reaction which is exothermic, generating a fusion temperature of around 300° C. This is still below the melting point of the arsenic trisulfide recovered as a precipitate at outlet 4. Reaction can be performed under atmospheric pressure.
  • Mixtures of different solid chalcogenides can be obtained, as starting materials for glasses of predetermined composition, from combinations of metal or metalloid sulfides, selenides and tellurides treated in the manner described.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Glass Compositions (AREA)
  • Physical Vapour Deposition (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
US06/626,053 1983-06-30 1984-06-29 Process for producing substances optically transparent to infrared rays Expired - Lifetime US4557914A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT67715A/83 1983-06-30
IT67715/83A IT1161486B (it) 1983-06-30 1983-06-30 Metodo per la produzione di materiali con trasparenza ottica nell'infrarosso

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US4557914A true US4557914A (en) 1985-12-10

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US06/626,053 Expired - Lifetime US4557914A (en) 1983-06-30 1984-06-29 Process for producing substances optically transparent to infrared rays

Country Status (12)

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US (1) US4557914A (da)
EP (1) EP0130594B1 (da)
JP (1) JPS6021822A (da)
AT (1) ATE29706T1 (da)
AU (1) AU553297B2 (da)
BR (1) BR8402970A (da)
CA (1) CA1227320A (da)
DE (2) DE130594T1 (da)
DK (1) DK163295C (da)
ES (1) ES8606214A1 (da)
IT (1) IT1161486B (da)
NO (1) NO158297C (da)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4869893A (en) * 1987-08-10 1989-09-26 Hughes Aircraft Company Preparation of high purity compounds of sulfur, selenium, and tellurium
US4942144A (en) * 1989-01-23 1990-07-17 Iowa State University Research Foundation, Inc. Infrared transmitting glasses with high glass transition temperatures
US5077239A (en) * 1990-01-16 1991-12-31 Westinghouse Electric Corp. Chalcogenide glass, associated method and apparatus
US5227149A (en) * 1991-10-08 1993-07-13 Sullivan Thomas M Process for making silicon monosulfide and aluminum sulfide
US5549971A (en) * 1986-08-18 1996-08-27 Clemson University Laser assisted fiber growth
US5779757A (en) * 1996-06-26 1998-07-14 The United States Of America As Represented By The Secretary Of The Navy Process for removing hydrogen and carbon impurities from glasses by adding a tellurium halide
US20060239882A1 (en) * 2003-01-31 2006-10-26 Seo Dong-Kyun Preparation of metal chalcogenides from reactions of metal compounds and chalcogen
US20070074541A1 (en) * 2003-10-10 2007-04-05 University Of Southampton Synthesis of germanium sulphide and related compounds
US10191186B2 (en) 2013-03-15 2019-01-29 Schott Corporation Optical bonding through the use of low-softening point optical glass for IR optical applications and products formed

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015083124A1 (en) 2013-12-04 2015-06-11 King Abdullah University Of Science And Technology Apparatuses and methods for combustion and material synthesis

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671739A (en) * 1949-06-22 1954-03-09 Bell Telephone Labor Inc Plating with sulfides, selenides, and tellurides of chromium, molybdenum, and tungsten
US3218204A (en) * 1962-07-13 1965-11-16 Monsanto Co Use of hydrogen halide as a carrier gas in forming ii-vi compound from a crude ii-vicompound
US3224913A (en) * 1959-06-18 1965-12-21 Monsanto Co Altering proportions in vapor deposition process to form a mixed crystal graded energy gap
US3224912A (en) * 1962-07-13 1965-12-21 Monsanto Co Use of hydrogen halide and hydrogen in separate streams as carrier gases in vapor deposition of ii-vi compounds
US3664866A (en) * 1970-04-08 1972-05-23 North American Rockwell Composite, method for growth of ii{11 {14 vi{11 {0 compounds on substrates, and process for making composition for the compounds
US4066481A (en) * 1974-11-11 1978-01-03 Rockwell International Corporation Metalorganic chemical vapor deposition of IVA-IVA compounds and composite
US4447469A (en) * 1982-06-10 1984-05-08 Hughes Aircraft Company Process for forming sulfide layers by photochemical vapor deposition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3657006A (en) * 1969-11-06 1972-04-18 Peter D Fisher Method and apparatus for depositing doped and undoped glassy chalcogenide films at substantially atmospheric pressure
DE2648702C3 (de) * 1976-10-27 1980-08-21 Jenaer Glaswerk Schott & Gen., 6500 Mainz Infrarotdurchlässige Lichtleitfaser aus sauerstoffarmem bzw. sauerstofffreiem GUs und Verfahren zu ihrer Herstellung
JPS589844A (ja) * 1981-07-08 1983-01-20 Hitachi Ltd 赤外光フアイバ
JPS57149835A (en) * 1981-03-06 1982-09-16 Hitachi Ltd Manufacture of infrared fiber

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671739A (en) * 1949-06-22 1954-03-09 Bell Telephone Labor Inc Plating with sulfides, selenides, and tellurides of chromium, molybdenum, and tungsten
US3224913A (en) * 1959-06-18 1965-12-21 Monsanto Co Altering proportions in vapor deposition process to form a mixed crystal graded energy gap
US3218204A (en) * 1962-07-13 1965-11-16 Monsanto Co Use of hydrogen halide as a carrier gas in forming ii-vi compound from a crude ii-vicompound
US3224912A (en) * 1962-07-13 1965-12-21 Monsanto Co Use of hydrogen halide and hydrogen in separate streams as carrier gases in vapor deposition of ii-vi compounds
US3664866A (en) * 1970-04-08 1972-05-23 North American Rockwell Composite, method for growth of ii{11 {14 vi{11 {0 compounds on substrates, and process for making composition for the compounds
US4066481A (en) * 1974-11-11 1978-01-03 Rockwell International Corporation Metalorganic chemical vapor deposition of IVA-IVA compounds and composite
US4447469A (en) * 1982-06-10 1984-05-08 Hughes Aircraft Company Process for forming sulfide layers by photochemical vapor deposition

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5549971A (en) * 1986-08-18 1996-08-27 Clemson University Laser assisted fiber growth
US4869893A (en) * 1987-08-10 1989-09-26 Hughes Aircraft Company Preparation of high purity compounds of sulfur, selenium, and tellurium
US4942144A (en) * 1989-01-23 1990-07-17 Iowa State University Research Foundation, Inc. Infrared transmitting glasses with high glass transition temperatures
US5077239A (en) * 1990-01-16 1991-12-31 Westinghouse Electric Corp. Chalcogenide glass, associated method and apparatus
US5227149A (en) * 1991-10-08 1993-07-13 Sullivan Thomas M Process for making silicon monosulfide and aluminum sulfide
US5779757A (en) * 1996-06-26 1998-07-14 The United States Of America As Represented By The Secretary Of The Navy Process for removing hydrogen and carbon impurities from glasses by adding a tellurium halide
WO1999007645A1 (en) * 1996-06-26 1999-02-18 The Government Of The United States Of America Represented By The Secretary Of The Navy Process for removing hydrogen and carbon impurities from glasses
US20060239882A1 (en) * 2003-01-31 2006-10-26 Seo Dong-Kyun Preparation of metal chalcogenides from reactions of metal compounds and chalcogen
US7393516B2 (en) * 2003-01-31 2008-07-01 Seo Dong-Kyun Preparation of metal chalcogenides from reactions of metal compounds and chalcogen
US20070074541A1 (en) * 2003-10-10 2007-04-05 University Of Southampton Synthesis of germanium sulphide and related compounds
US10191186B2 (en) 2013-03-15 2019-01-29 Schott Corporation Optical bonding through the use of low-softening point optical glass for IR optical applications and products formed

Also Published As

Publication number Publication date
DE130594T1 (de) 1985-08-29
EP0130594A1 (en) 1985-01-09
AU2723484A (en) 1985-01-03
BR8402970A (pt) 1985-05-28
NO158297C (no) 1988-08-17
DE3466207D1 (en) 1987-10-22
DK299684D0 (da) 1984-06-19
EP0130594B1 (en) 1987-09-16
NO158297B (no) 1988-05-09
DK163295C (da) 1992-07-06
ATE29706T1 (de) 1987-10-15
DK299684A (da) 1984-12-31
IT8367715A0 (it) 1983-06-30
JPS6021822A (ja) 1985-02-04
DK163295B (da) 1992-02-17
NO842438L (no) 1985-01-02
AU553297B2 (en) 1986-07-10
IT1161486B (it) 1987-03-18
CA1227320A (en) 1987-09-29
ES533541A0 (es) 1986-04-01
ES8606214A1 (es) 1986-04-01

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